28.03.2016
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Corrosion is a process by which a material may gradually wear away, usually by a chemical action.
The cost of poor corrosion resistance is dramatic, as determined in a 2002 study by the U.S. A number of chemistries and cure mechanisms are currently employed in corrosion protective coatings. The industry has been trending toward more environmentally friendly, water-based compositions, including aqueous alkyds, epoxy esters, polyesters and polyurethanes.
Current uses for direct-to-metal corrosion-resistant coatings include those that are applied to pipe and tubing, fencing, coil stock and metal drums.
A long-term project was initiated to better understand the corrosion protective performance of coatings formulated from various types of acrylate monomers and oligomers. The oligomer test series was comprised of varied backbone structures, including epoxy acrylates, polyester acrylates and acrylated acrylics. Improved corrosion resistance was observed with coatings formulated from aliphatic (ALUA) and aromatic (ARUA) urethane acrylate oligomers. Figure 6 illustrates the relative corrosion protection contribution of the various oligomer chemistries. Testing of commonly used monomers indicated that they impart less corrosion protection compared to oligomers – possibly due to significantly lower molecular weight.
Combating the corrosive impact of salt spray at elevated temperature was the initial focus of this project, but outdoor applications face additional degrading elements – namely UV irradiance, temperature, and moisture.
QUV testing was conducted on the most corrosion-resistant aliphatic urethane oligomer (ALUA) in the previous study to establish a baseline (CN9030). The prior corrosion resistance study suggests that with some exceptions, aromatic urethane acrylate oligomers (ARUAs) may offer performance advantages over ALUAs. The chemistries that are used for corrosion protection vary widely, including polyurethanes, acrylics and alkyds. It is widely known that ARUAs do not resist yellowing as well as ALUAs, and the addition of a HALS to coatings based on ARUAs can dramatically improve weathering resistance, making them less prone to yellowing. Our September issue focuses on sustainable solutions, specialty chemicals, architectural coatings and the latest pigment technology.
Chrome plating is a process that involves the electroplating of a thin veneer of chromium onto an underlying metal. Decorative chrome plating is sometimes called "nickel-chrome" because it involves electroplating nickel onto the object before plating the chrome (it sometimes involves electroplating copper onto the object before the nickel, as well). In addition to the length of the process, chrome plating is not environmentally friendly due to the use of hexavalent chromium.
PVD is the deposition of a metal onto a substrate through changes in the physical state of the metal (solid to gas to solid). Thermal Evaporation is the deposition of a metal via thermal vaporization in a vacuum environment. Sputtering is the deposition process where atoms on a solid metal target are ejected into a gas phase due to bombardment of the material by high-energy ions. The main target of the UV-curable coating development for PVD was to provide an alternative to traditional inorganic chrome with a layer system of organic and inorganic materials.
Wide range of appearances: PVD equipment suppliers are able to achieve numerous metal colors by using a mixture of various metals and gases within the vacuum chamber (see later section on limitations of color by PVD process). Additional features of UV + PVD coatings: Suitable for pad or screen printing, gluing and realization of filigree surface structure (brushed effects) on plastics, as well as metal substrates.
Increased throughput: From applying basecoat until packaging of the finished part, the cycle time for PVD can be as short as 15 minutes.
Challenges associated with the development of each of these layers and the processing of each are explained in the following paragraphs. Furthermore, achieving adhesion of the metal to plastic can be more difficult than with a basecoat layer. Formulation of the basecoat must optimize its acceptance of PVD metal (adhesion), while avoiding stress cracking. Known paintability issues must be considered: adhesion for multiple substrate part design vs. UV-cure still incorporates residual heat due to a heated convection, IR flash or combination prior to the UV cure. Although initial topcoat adhesion to chrome is relatively easy to achieve, maintaining that adhesion after humidity, water immersion, thermal cycling and weathering can be a bigger challenge.
In a direct comparison with chrome, PVD samples with a UV-curable topcoat show performance equal to decorative chrome plating. UV inherently has higher crosslink density and hardness than thermal cure technology and can achieve better scratch and abrasion vs. Processing techniques such as cure in an inert environment (like nitrogen) can minimize oxygen inhibition and improve hardness. Substrate: A wide variety of thermoset and thermoplastic substrates can be coated with a UV basecoat to achieve a bright finish. Substrate tooling and surface quality affect the appearance of the finished part as the basecoat may not cover all surface defects.
Finally as with any pigmented system, even pigment distribution and preventing flocculation or mottling is a challenge. Demand for plastic products and alternatives to traditional electroplated systems continue to grow.
Read the latest print edition of Plastics Decorating on your desktop, smartphone or tablet. We invite you to browse the resources on this site and discover the wealth of solutions that we offer for your colorant needs and challenges.
Or, contact us for a more detailed discussion on how we can improve your coloring or processing results. Spectratek UV lamps meet or exceed the highest international standards for performance and safety.
With an emphasis on situations needing high performance and fast production throughput industries like electrical components suppliers, product assembly producers, automotive and construction turn to Novagard Solutions for meeting their manufacturing challenges.
These products are scientifically formulated to meet your specified performance requirements.
Novagard is a leading manufacturer of these silicone greases and compounds, which are ideally suited for use in hostile environments and critical lubrication applications. These range from alkyd and epoxy ester coatings that are baked or air dried to promote crosslinking.
High solids or powder coatings based on vinyl, polyester, or epoxy ester compositions are also favorable alternatives. In 2000 and 2005 surveys conducted by the National Paint and Coatings Association, waterborne coatings in direct-to-metal applications rose from 13% to 35%.


These coatings are also used in rigid packaging applications, where they shield the inks on 2- and 3-piece beverage cans and provide environmental protection for the cans during processing, shipping and handling. This was accomplished by coating cold rolled steel (CRS) panels and subjecting them to a controlled corrosive environment. Q ultraviolet (QUV) accelerated weathering testing intensifies the effect of these factors on coated specimens. This yellowness index (YI) was measured initially and every 100 h up to 1000 h per ASTM E313-98. This oligomer was tested neat (without additives), with the addition of a HALS and with a mixture of a HALS and corrosion-inhibiting pigment (CIP). Aromatic epoxy acrylates contribute mid-range performance to corrosion protective coatings. Over coating an ARUA-based coating with one based on an ALUA may produce a weathering advantage compared to the use of the ARUA-based coating alone. Color and appearance effects are limited with traditional chrome electroplating, and successful "paint-on-chrome" applications are expensive and highly proprietary.
As development of UV-curable coatings for PVD has progressed, so has the understanding of the process and its unique capabilities and applications. Chrome plating can be classified as either "hard chrome plating" or "decorative chrome plating". The nickel plating provides smoothness, much of the corrosion resistance and most all of the reflectivity associated with chrome appearance. For most automotive applications, a very thin layer of metal, approximately 600-1000 angstroms, is deposited onto the basecoat layer. The bombardment releases atoms from the metal target, which are deposited directly onto the part within the vacuum chamber. This involves applying a UV basecoat on the substrate, followed by a PVD metal layer and, lastly, the UV protective topcoat.
This technology also lends itself to a "chrome" daytime look, but with soft backlit colors for night time driving, e.g.
In addition, the top coat can be modified to provide a satin or low-gloss finish, which has become popular for interior automotive applications. Limitations in plastic design for chrome plating are associated with how the plating is attracted to the part and where the plating may have more tendencies to build up.
With no hexavalent chromium exposure or disposal, no hazardous waste to report and full recyclability (due to the metal layer thickness in a nanometer scale), all work with UV-curable coatings to make for a much safer production environment. In contrast, traditional chrome plating can take up to 2.7 hours (dependent upon the desired chrome thickness).
It is a skilled art, and there is limited number of finishers with the knowledge and expertise to do this with consistent success. A successful coating must have excellent adhesion to a variety of substrates, as well as be able to accept PVD metals.
These technologies each have different processing windows that must be optimized to achieve acceptable basecoat-PVD-topcoat system performance. This can vary from a thin layer of in-chamber siloxane to a thicker thermal or UV-curable topcoat. In order to balance proper adhesion to chrome and maximize abrasion-, scratch-, moisture- and chemical-resistance, it is imperative to find the balance formulation between too rigid to get adhesion and too soft to pass resistance testing. This too is an exercise in economics because the added cost of creating an inert environment may not justify the added performance. From an application standpoint, sharp edges, deep recesses and location of parting lines can affect the success and optimization of the application (not only for paint, but also for the PVD process).
Finally, the nature of the racking should be noted to consider that metal racking could interfere with the PVD process by arcing or attraction of the PVD metal to a particular area. For injection molding, it is important to choose a substrate with melt and flow characteristics that adequately match the part design and can mold in desired cycled times. Coatings with weathering requirements will need more UV energy and intensity to cure properly. Markets once driven by cost per piece and "green" or environmental concerns now are giving way to demand for functional capability. Don't miss this chance to read about new technologies, tips on expanding your business and the latest developments in the plastics decorating and assembly industry – absolutely FREE!
They are designed and built in North America for use worlwide on all current ultraviolet light curable fillers, base coats (primers), top coats, and clear coatings on: metal (including aluminium), wood, glass, plastic, concrete and composite. Examples are common – from marine, structural and architectural applications, to residential fencing and automobiles. Also used are solventborne two-part coatings employing polyurethanes or latexes based on vinyl, acrylic or styrenic combinations. The same survey showed growth in 100%-solids coatings based on acrylate monomers and oligomers. A Bisphenol A aromatic (AR) epoxy acrylate, CN120, was used as the control in this round of testing and received a rating of 2. SR506 and SR531, being mono functional, are low in crosslink density, making them subject to moisture attack. A series of pigments was evaluated individually and in combination, using SR833S as a vehicle. Additionally, a panel was prepared in which (2) 1-mil coatings were applied, with a cure cycle following each. As shown in Figure 10, the sample with the HALS achieved a YI that represented a significant improvement over the baseline oligomer.
QUV testing was performed in which a baseline ARUA was evaluated against an ARUA containing a HALS and an ALUA containing a HALS. It was observed in this study that the urethane acrylate oligomers provide the best corrosion protection. Hard chrome plating is chrome plating that has been applied as a fairly heavy coating (usually measured in thousandths of an inch) for wear resistance, lubricity, oil retention and other "wear" purposes. A wide variety of metals can be deposited, including aluminum, chrome, titanium, stainless steel, nickel chrome, tin, etc. It is placed inside a tungsten coil; the number of coils can vary depending on size of the chamber. Although this same color effect can be achieved by using a chrome plating process, the part first must go through a lengthy preparation process. This demands that molds must be maintained in optimum condition and polished regularly to ensure the surface of the parts are free from defects. There are inherent performance limitations of a direct metalized system, such as less resistance to moisture (or a greater tendency to delaminate). Chrome is more durable than aluminum and is preferred for exterior applications; thus a basecoat must be formulated specifically to PVD chrome metal. Furthermore, as UV coatings are line-of-sight cure, both part design and part racking in relation to lamp configuration need to be considered to ensure adequate cure of the coating and avoid any areas of tackiness or uncured coating.
The substrate surface is critical to the film formulation process and for obtaining good adhesion of the basecoat to the substrate or for PVD to substrate in direct substrate-to-metallization applications. UV coatings tend to be inherently lower in viscosity, resulting typically in lower sag points. Physical Vapor Deposition, when combined with UV-curable coatings, offers design engineers an almost unlimited color and appearance palette, while simultaneously offering consumer safety and innovative functionality.
Importance of Pigment and Dispersion Characterization for Optimum Cure and Performance in UV-Curable Stains, Inks and Coatings.
The paper was presented at ANTEC 2014 as part of the SPE Decorating & Assembly Division sessions.
Following ASTM B117 protocol, the test panels were exposed for 21 days, then visually inspected and given a subjective rating from 1 to 5, with 5 being the best. Despite its hydrophobic nature, the polybutadiene acrylate, CN307, performed very poorly (1 rating).


However, the study showed that aliphatic urethanes based on polyester or polycarbonate polyols offer significantly improved corrosion resistance. In contrast, SR351 and SR295 are higher in functionality, making the film too brittle when cured, resulting in poor adhesion and surface cracking.
As shown in Figure 8, proprietary pigment 2, at 5% by weight, achieved a perfect rank of 5 based on ASTM B117 exposure. A UVA 340 bulb was used because its output, which centers around 340 nanometers, closely replicates that of sunlight.
The results, as shown in Figure 11, are as expected – the ALUA with a HALS is superior to the ARUA with a HALS, which is superior to the baseline ARUA. From 2000 to 2004, distributions of solventborne direct-to-metal coatings decreased from 84% to 61%. Although aromatic urethanes are generally superior to aliphatics, there are exceptions based on backbone structure. The addition of corrosion-inhibiting pigments did not appear to affect weathering resistance. Some examples would be hydraulic cylinder rods, rollers, piston rings, mold surfaces, thread guides, gun bores, etc. When you look at a decorative chrome-plated surface, such as a wheel or truck bumper, most of what you are seeing is actually the effects of the nickel plating. Legal obligations include permitting, pretreatment of waste water, hazardous waste manifesting, waste accumulation by permit and "cradle-to-grave" ownership of waste and byproducts. The PVD layer can be deposited by a variety of methods, including, but not limited to, thermal evaporation, cathodic arc, sputtering, pulsed laser deposition and electron beam deposition. Once the chamber is pumped down to a vacuum, the tungsten filaments are heated to 1200 degrees Fahrenheit (for aluminum), enough to melt the metal. Both pure elements and alloys can be used with either method, but will be deposited differently. Some parts are direct metalized; however, this requires a higher or more expensive grade of thermoplastic (substrate) to accomplish. Thus, the number of relevant applications for direct metallization to plastic substrate would be limited primarily to interior applications.
Due to chrome being a very rigid metal, many commercial basecoats that work well with aluminum may not work with chrome. In some instances, there is investigation or proposal to not use a topcoat, whereby a very thick layer of PVD will be used.
Uncured material can have a negative effect in the PVD chamber, especially on pumps and in pulling the vacuum.
The substrate surface should be characterized to the extent necessary to obtain a reproducible film. Stress affects surface tension of the part – the more stress, the less paintable the part will be. It needs to be rigid enough for the deposited PVD to stay aligned to keep the highly reflected surface, but flexible enough to not crack when flexed. When incorporating tints into the system, careful consideration must be given to formulation and rheology to ensure there is consistency of film build and no collection points. However, monomers are often a necessary component of coating formulations, and the data in Figure 7 shows that difunctional monomers seem to offer more protection owing to a balance of cure film properties (M3 in Figure 7). Also observed was that the proper selection and use of corrosion-inhibiting pigments can greatly enhance performance of acrylate-based protective coatings. The chrome adds a bluish cast (compared to the somewhat yellowish cast of nickel), protects the nickel layer against tarnish, minimizes scratching and symbiotically contributes to corrosion resistance. Finishers have been asking for a safer, greener, quicker alternative without sacrificing appearance and performance. The power to the filaments then is increased to roughly double the temperature, and the metal is evaporated. For elements, the final deposit is thermal evaporative and sputtering, but due to the method of deposition, the appearance can be slightly different. Stress cracking is a very common failure mode if the basecoat is not formulated specifically for PVD chrome. For exterior purposes, there are currently OEM-approved thermal, two-component coatings and thermal powder coatings on the market. Care must be taken that the surface properties are not changed by cleaning processes or recontamination, either outside the deposition system or inside the deposition system during processing. It also should be noted that this may not manifest itself immediately, but may shorten the lifetime of the part and finish. This becomes more of a challenge with complex 3D parts or when part designs incorporate sharp edges. Subsequently, blends of oligomers and monomers were evaluated in an effort to maximize performance.
Tricyclodecane dimethanol diacrylate (SR833S) demonstrated the best corrosion resistance with an ASTM B117 rating of 2.
A key point to remember – without a brilliant, leveled nickel undercoating, you will not have a reflective, decorative chrome surface. For alloys, with thermal evaporation, the metal with the lowest melt temperature will evaporate first and deposit onto the part. Chrome and its alloys will work for exterior applications, but are rigid and susceptible to cracking on flexible substrates. Thus said, with PVD and UV processing, there still needs to be consideration of best fit of substrate to the process.
Many thermal cure coatings lack the proper cross link density to be used with the more rigid metals. Also, as it is economically desirable to recycle or to use regrind material, it should be appropriately managed as not to disrupt paintability or performance.
Another challenge with tinting clear coats for PVD is the fact that the highly reflective surface easily will show any incompatibilities (haze) or poor dispersion of the pigment. Where viscosities were prohibitively high, 50% acetone mixtures were made to facilitate handling and flashed off prior to curing.
It is possible that a second layer fills any voids or defects in the first, providing a higher-quality coating.
It is important to incorporate proper tint dispersions to obtain the clarity and appearance of tinted metal. The results suggest that applying an ALUA coating over an ARUA-based formulation may be a viable means of optimizing corrosion protection and weathering resistance.
With nickel chrome, for example, nickel melts around 2,500 degrees Fahrenheit and chrome has a melting point around 3,400 degrees Fahrenheit. Consumer safety benefits include no change in substrate breaking strength when UV + PVD coatings are employed, no splinters or flying metal particles upon impact, etc.
Typically, dyes would be considered ideal for such clarity, but dyes do not provide adequate light fastness and color stability to withstand the rigorous performance targets.
When thermally evaporated, the nickel will melt, evaporate and condense on the parts, followed by the melting, evaporation and deposition of the chromium: two distinct layers of metal. Potential applications include airbag emblems, overhead components, body security parts, etc.
However, not only do the long bake times hinder productivity, the high temperatures required to cure the powder will not work with most thermoplastic substrates. With sputtering, the metals will deposit at the same time to have a true nickel-chrome alloy. An ultraviolet-cured coating can satisfy both the environmental and process requests of the finishers and OEMs.



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